Composition containing wood oil ob



phur, selenium, sulphur chloride, etc.

Patented May 18,

coMrosrnoN comma woon on. on orrrcrcs on.

William Krumbhaar, New York, Y.

No Drawing. Application February 23, 1940, Serial No. 320,510

1; Claims. (Cl. 106-218) This invention relates to surface coatings and methods of producing the same and materials useful therein, and particularly to wood oil or oiticica oil-containing surface coatings of low viscosity, which dry with the characteristics of these oils without, however, their wrinkling tendencies.

In the past, various types of wood oil or oiticica oil-containing surface coatings have been produced. The production of such compositions of desirable properties has offered difliculties in a number of difierent directions. paint vehicles, it has always been diflicult to hit upon the right compromise between a glossy and somewhat tacky oil and a flat and good drying.

product. In printing ink oils, the right medium had to be found between products of sufficient gloss with good pigment compatability on'the one hand, and products of high gloss without a varnish making, and for the manufacture of surface coatings, but the di and triglycerides are subject to gelation in very short periods of time when treated at the temperatures required in such processes. This is true whether such di or triglycerides are heated by themselves or in the I presence of esterifying components. In the case of phthalic resins, it has always been a problem to incorporate 'larger amounts of wood oil or oiticica oil because the resulting products were either not gas-proof, or if made gas-proof, they I assumed an impracticably high viscosity.

Many attempts .have been made to secure the desired effect by the use of special heating devices or heating methods, by blending the two oils with other oils or'resins, by making small additions of substances which retard gelatinization, such as phenols, naphthol. guaiacol, sul- In all cases, however, some compromise was necessary. If the surface coating materials produced with the In the case of oils hereinbefore mentioned according to prior art methods, possessed low viscosity, were quick drying and formed hard tack free films, they showed pronounced tendency to wrinkle and were not gas-proof when subjected to the customary gas test. If, on the other hand, the coatings proved to be non-wrinkling under adverse drying conditions, they invariably possessed the formed-a soft, sticky film. In actual practice, the properties of wood oil or oiticica oil-containing surface coatings varied between the two extremes mentioned, resulting in compromise products which were never entirely satisfactory.

Among the objects of the present invention is the production of wood oil or oiticica oil-containing surface coatings which eliminate the'difliculties of the prior art, and avoid such prior art compromise between viscosity and drying properties on the one hand and wrinkling tendencies on the other. c

Other objects include the production of novel types of derivatives which can be utilized in surfacecoatings to produce the desired results set forth above. Still further objects and advantages will appear from the more detailed description set forth. below, it being understood that this more detailed description is given by way of explanation and illustration only and not by way of limitation, since various changes therein may be made by those skilled in the art without departing from the scope and spirit of the present invention. In accordance with the present invention, it

has been found that the monoglycerideof elaeostearic acid or the monoglyceride of wood oil and oiticica oil fatty acids can be heated for extended periods of time at temperatures higherthan those which would cause gelation of elaeosteariotriglyceride, of wood oil or of oiticica oil, with only a slight increase in viscosity of the monoglyceride, and without any tendency to gelatinization, and it has been further found that if the monoglycerides which have been heat treated above the gelation temperature, are incorporated into surface coatings, such coatings have low viscosity and dry with the characteristics of wood oil or oiticica oil, but without their tendencies to form wrinkles. The heat treated mono-,glycerides of the, desired characteristics produced in accordance with the present inventionmay desirablybe referred to as non-wrinkling or gas-proof, or both terms may be utilized to describe such products. In order to obtain the non-wrinkling, gas-proof modification of the monoglycerides, they should be heated either by themselves, or in the absence of esterifying components which react with the free hydroxyl groups of the monoglycerides. saponiflable components like coumarone resins,

or neutral ester-like substances like fatty oils may-be present without interfering with the formation of the modification desired,- and retarders of gelatinization may alsobe present.

Neutral, un-

elaeostearic acid, is considered to have a molec-' ular weight of 266, and the triglyceride the molecular weight of 836, equivalent proportions are 22 parts of glycerine to 100 parts of triglyceride to form 122 parts of the monoglyceride of a molecular weight of 340. In actual practice, a slight excess over this quantity is used as, for example, 22.5 parts of glycerlne to 100 parts of wood oil. The ratio of glycerine to triglyceride as given above is the preferred one, but is subject to variation to some degree. Reduction in the amount of glycerine will still result in the formation of monoglyceride, though to a lesser and, therefore, less desirable extent. Increase in the amount of the glycerine favors the formation ofmonoglycerides, but may result in free glycerine remaining unabsorbed in the reaction mixture, so that generally not more than 225, parts of glyceride to 100 parts of triglyceride will be used. To facilitate the alcoholysis, a small amount of a catalyst like calcium glycerate or litharge is desirably added. A suitabl reaction temperature is 2'i0250 C., and with'the ratios given above about 2 hours heating is required until all of the glycerine is taken up. The conditions given above for the production of the monoglycerides are those most desirably employed, but the formation of monoglycerides is a progressive reaction and, therefore, some flexibility in reaction temperatures and times is allowable in actual operation.

The monoglyceride produced in any desirable wayas, for example, in the manner set forth above, is then heat treated to convert it into the non-wrinkling, gas-proof modification, which imparts the same properties to the coating compositions into which such modificationis incor-' porated. The conversion into the non-wrinkling, gas-proof modification is a progressive reaction, the times of treatment and the temperatures at which such treatment is carried outwbeing corelated. The extent to which conversion is obtained depends on the time and temperature treatments. Generally it may be saidthat the monoglycerldes should be treated at temperatures higher than 240 C. for a period suflicient to give the desired properties, which is generally not less than 2 hours. Longer time or treatment at lower temperatures will give efi'ects comparable with those obtained for shorter time at higher temperatures. Convenient time and temperatures for the heat converted monoglycerides;

are, for example, 6 hours at 250, 4 hours at 260 or most desirably, 2 hours at 270. These time treatments and temperares,vhowever, are not limiting, and in some cases both longer heat treatments and higher temperatures may be utilizei. Thus wood oil monoglyceride can be convert d by heat treatment at 270 for '6'hours .Witho t gelation. Desirably the heat treatment is carried out for a suflicient time to carry the conversion to completion.

The conditions of heat treatment to produce the non-wrinkling, gas-proof modification may vary to some extent depending on whether the monoglyceride is heated by itself, or whether other non-esterifying components as indicated above are present. The presence of some added components which do not interfere with the for mation of the non-wrinkling, gas-proof modification may, however, require longer periods of time treatment at the ranges of temperature indicated in order to get conversion to the extent desired. The temperature employed, however, in any event should not be so high as to undesirably affect the monoglyceride or other components present.

Such heated products resulting from the present invention are of great practical importance, because it becomes possible to exploit fully the merits and benefits of wood oil or oiticica oil in paint vehicles, printing ink oils and synthetic resins, such as those of the alkyd type, resulting in compositions of relatively low viscosity with the drying characteristics of wood oil or oiticica oil, but without the wrinkling tendencies of such oils. The heat treated monoglyceride are capable of utilization for such purposes in a wide I variety of ways.

The free hydroxyl groups of the heat treated monoglyceride are desirably re-esterified by suitable organic acids, desirably used in amounts which are equivalent to their molecular weights or their acid values. Of practical importance among the acidic substances used there may be mentioned particularly rosin, copals, fatty acids, maleic anhydride, phthalic anhydride and mixtures thereof. Various types of acidic substances may be used to produce particular results. Thus the esterification of the free hydroxyl groups by resin is desirable from the economic point of view and because the solubility of the product is improved. Fossil gums, especially Congo copal, are very suitable materials to be combined with the monoglyceride, because they create water- Proof characteristics and resistance to abrasion. Some natural gum as, for instance, Manila and Loba copals, do not require any pre-treatment or preparation before being utilized for the treatment of the modified monoglyceride. Other fossil gums, however, are desirably given a treatment such as fusion and decomposition by destructive distillation to prevent gelatinization, or the copals may be subjected to other methods of depolymerization, such as by mastication.

Fatty acids are desirable for re-esteriflcation because they esterify readily, and they offer a wide variety of different types, among which may be mentioned linolic, linolenic, octo dekadienic acid, etc. Generally speaking, all higher fatty acids, present in drying oils, are useful. However, it should be noted that wood oil or oiticica oil fatty acidsare not desirably used for this purpose, because the reaction mixture Will gelatihize during re-esterification. Polybasic organic compounds, especially the anhydrides of maleic and phthalic acids lend themselves excellently for the neutralization of the heat treated monoglyceride, and even small amounts impart to the Products the well-known characteristics of maleic and phthalic resins. Other polybasic aliphatic and aromatic acids which are useful include succinic, fumaric, adipic, sebacic, citric.

In ca ying out the method ofthe invention, it should beborne in mind that re-esterification is usually connected with a large increase in the size and weight of the glyceride molecules, which in turn may manifest itselfby an increase in vishydroxyl groups of the monoglyceride is conicharacter, which are used as the customary in gredients in surface coating materials. Among the materials suitable to extend the esterified pleted. The product obtained in this way is then converted into a short oil phthalic resin by heating it with 20 parts of glycerine and 40 parts of phthalic anhydride for several hours at 240.

The resulting resin yields scratch and marproof product, ester gum, coumarone resin, .or the commercial phenolic and maleic acid resins may be first mentioned. Volatile solvents can also be used for the same purpose. An enormous variety of useful substances is produced in this way. and to all of them are imparted the properties of wood oil or oiticica oilwithout diminishing gloss or increasing viscosity substantially.

- Phthalic resins can also be used for the extension. of the esterified. monoglyceride-and more particularly the straight glycerol phthalate is applied to produce a short oil wood oil modified resin. Short oil wood oil modified phthalic resins. although desirable on account of their surface hardness and their waterproofness have heretofore been difficult to make. In making such resins there always was a rapid rise in viscosity with a strong tendency to gelation, and this danger could be checked only by large additions of other oils. Therefore, the highest proportion of wood oil which could be incorporated according to prior art methods was only 30% wood oil in the oily component, and such compositions were unsatisfactory. The methods-of the present invention a permit a considerable increase in wood oil components in such resins up to and beyond 50% and even up to straight wood oil phthalics.

. Another method of extending the re-est-erified monoglyceride consists in blending it with various types of semi or full drying oils in a more or less polymerized state. This method in actual practice means the modification ofoils in a new way by imparting the good characteristics of wood oil without its short-comings, and has particular importance in many directions as, for example, in

- the production of litho or paint oils modified with mixed esters of abietic acid and/or copal acids and/or dibasic acids like phthalic or maleic acids.

To form the gas-proof compounds. the

coatings, has low viscosity and is particularly suitable for automobile finishes.

(3) 200 parts of wood oil are combined with 45 parts of glycerine and heated in the same manner described in Examples land 2 to form a gas-proof monoglyceride. After the heat treatment at 270, the temperature is lowered to 200 and 18 parts of phthalic anhydride are added By raising the heat to 240 the phthalic anhydride combines easily with the monoglyceride, and now the remaining excess of the free hydroxyl groups is neutralized by the addition of 67 parts of linseed oil fatty acids. The batch is held at 260 until an acid value of 12 and a viscosity of X on the Gardner scale is reached. The product, obtained in this way is outstanding as a paint vehicle by its drying speed, penetration properties and water resistance. i (4) The procedure is carried out according to Example 3; however, the wood oil is replaced by oiticica oil.

Having thus set forth my invention, I claim: 1. A composition containing a non-gelatinizing organic carboxylic acid ester of a non-wrinkling, gas-proof monoglyceride of a component selected from the group consisting of elaeostearic acid and the mixed fatty acids of wood and oitlcica oils produced by the process of claim 10.

2. A composition containing a resin acid ester of a non-wrinkling, gas-proof monoglyceride of a cmponent selected from the group consisting of elaeostearic acid and the mixed fatty acids of wood and oiticica oils produced by the process of claim 15.

3. A composition containing a non-gelatinizing drying oil fatty acid ester ofa non-wrinkling.

and after that time 180 parts of fused Congo copal are added and the mixture is held at 280 for 23 hours. The acid value decreases slowly and as soon as it drops below 25 the batch is chilled back" with 600 parts'of bodied perilla oil. Instead of Congo copal, Manila copal may be used, or an equivalent amount of an acidic synthetic resin may be applied, as for instance, a rosin modifled incompletely esterified phenolic resin. The

resulting oil has excellent characteristics of adin this way is then heat treated for 2 hours at 270 to destroy wrinkling tendencies. After this is achieved, the temperature is lowered to 180 and 12 parts of maleic anhydride are added. whereupon the temperature is raised slowly again. At

220 80 parts of rosin are admixed by heating the batch up to 26 the neutralization of the free gas-proof monoglyceride of a component selected from the group consisting of elaeostearic acid and l from the group consisting of elaeosteariccacid and the mixed fatty acids of wood and oiticica oils produced by the process of claim 12, and a com patible extending agent in an amount to give desired viscosity to the composition.

6. A composition containing a non-gelatinizing organic carboxylic acid ester of a non-wrinkling,

" gas-proof monoglyceride of a component selected from the group consisting of elaeostearic acid and the mixed fatty acids of wood and oiticica oils produced by the process of claim 11, and an extending agent selected from the group consisting of neutral and esterlike oily and resinous substances.

7. A composition-containing a non-gelatinizing organic carboxylic acid ester of a non-wrinkling, gas-proof monoglyceride of mixed fatty acids of wood oil, produced by the process of claim 10.

8. A composition containing a non-gelatinizing organic carboxylic acid ester of a non-wrinkling, gas-proof monoglyceride of oiticica oil fatty acids produced by the process of claim 16.

9. A composition containing a non-gelatinizing organic carboxylic acid ester of a non-wrinkling,

gas-proof monoglyceride, of elaeostearic acid produced by the process of claim 10.

10 In a method of producing oil-containing surface coatings of low viscosity which dry with the characteristics of wood or oiticica oil but without their wrinkling tendencies comprising esterifying a non-wrinkling, gas-proof heat treated monoglyceride of a component selected from the group consisting of elaeostearic acid and the mixed fatty acids of wood and oiticica oils produced by heatin at a, temperature above 240 C. but below that which would undesirably affect the monoglyceride in the absence of esterifying components, with a non-gelatinizing organic carboxylic acid selected from the group consisting of drying oilmonobasic fatty acids and aliphatic and aromatic polybasic organic carboxylic acids.

11. I-n'a method of producing oil-containing surface coatings of low viscosity which dry with the characteristics of wood or oiticica oil but without their wrinkling tendencies comprising esterifying a non-wrinkling, gas-proof heattreated monoglyceride of a component selected from the group consisting of elaeostearic acid and 'the mixed fatty acids of wood and oiticica oils produced by heating at a temperature above 240 C. but below that which would undesirably afiect the monoglyceride in the absence of esterifying components, with a. non-gelatinizing organic carboxylic acid selected from the group consisting of drying oil monobasic fatty acids and aliphatic and aromatic polybasic organic carboxylic acids, and incorporating an extending agent selected from the group consisting of neutral and esterlike oily and resinous substances.

12. In a method of producin oil-containing surface coatings of low viscosity which dry with the characteristics of yvood or oiticica oil but without their wrinkling tendencies, the step which comprises heating a monoglyceride of a component selected from the group consisting of elaeostearic acid and the mixed fatty acids of wood and oiticica oils at a temperature above 240? C. but below that which would undesirably afiect the monogiyceride in the absence of esteritying components for a time dependent on said temperature sufficient to convert such monoglyceride into a non-wrinkling, gas-proof coating component.

13. In a method of producing oil-containing surface coatings of low viscosity which dry with the characteristics of wood or oiticica oil but without their wrinkling tendencies, the step which comprises heating a monoglyceride of a component selected from the group consisting of elaeostearic acid and the mixed fatty acids of wood and oiticica oils at a temperature above 240 C. but below that which would undesirably afiect the monoglyceride in the absence of esteriiying components for a time dependent on said temperature sufiicient to convert such monoglyceride into a non-wrinkling, gas-proof coating component, and esterifying the non-wrinkling, gas-proof monoglyceride with a non-gelatinizing organic carboxylic acid selected from the group consisting of drying oil monobasic fatty acids and aliphatic and aromatic poiybasic organic carboxylic acids.

14. In a method of producing oil-containing surface coatings of low viscosity which dry with the characteristics of wood or oiticica oil but Without their wrinkling tendencies, the step which comprises heating a monoglyceride of a component selected from the group consisting of organic carboxyiic acid selected from the group consisting of drying oil monobasic fatty acids and aliphatic and aromatic polybasic organic carboxylic acids, and incorporating an extending agent selected from the group consisting of neutral and esterlike oily and resinous substances.

. 15. In a method of producing oil-containing surface coatings of low viscosity which dry with the characteristics of wood 'or oiticica oil but without their wrinkling tendencies comprising esterifying a non-wrinkling, gas-proof heattreated monoglyceride of a component selected. from the group consisting of elaeostearic acid and the mixed fatty acids of wood and oiticica oils, with a non-gelatinizing organic carboxylic resin acid.

16. In a method of producing oil-containing surface coatings of low viscosity which dry with the characteristics of wood or oiticica oilbut without their wrinkling tendencies comprising esterifying a non-wrinkling, gas-proof heattreated monoglyceride of a component selected from the group consisting of elaeostearic acid and the mixed fatty acids of wood and oiticica oils, with a non-gelatinizing drying oil monobasic fatty acid.

1'7. In a method of producing oil-containing surface coatings of low viscosity which dry with the characteristics of wood or oiticica oil but without their wrinkling tendencies comprising esterifying a non-wrinkling, gas-proof heat treated monoglyceride of a component selected from the group consisting or eiaeostearic acid and the mixed fatty acids of wood and oiticica oils, with a non-gelatinizi-ng organic carboxylic acid selected from the group consisting of aliphatic and aromatic polybasic organic carboxylic acids.

18. In a method of producing oil-containing surface coatings of low viscosity which dry with the characteristics of wood or oiticica oil but without their wrinkling tendencies, the step consisting of heating a, monoglyceride of a component selected from the group consisting of elaeostearic acid and the mixed fatty acids of woodand oiticica oils at a temperature-above 240 C. but below that which would undesirably affect the monoglyceride in the absence of esterifyi-ng components for a time at least two hours,

suificient to convert such monoglyceride into a non-wrinkling, gas-proof coating component.

WHaLIAM I'KRUMBHAAR. 

